U.S. patent number 10,370,546 [Application Number 15/522,584] was granted by the patent office on 2019-08-06 for water/oil-repellent coating composition.
This patent grant is currently assigned to SUMITOMO CHEMICAL COMPANY, LIMITED. The grantee listed for this patent is SUMITOMO CHEMICAL COMPANY, LIMITED. Invention is credited to Atsushi Hozumi, Tomonori Miyamoto, Sayaka Sakurai, Yasuharu Shimazaki, Chihiro Urata.
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United States Patent |
10,370,546 |
Shimazaki , et al. |
August 6, 2019 |
Water/oil-repellent coating composition
Abstract
The object of the present invention is to provide a
water/oil-repellent coating composition for forming a film capable
of attaining both water/oil repellency and abrasion resistance. The
water/oil-repellent coating composition comprises: an organosilicon
compound (A) and a metal compound (B), wherein at least one first
hydrocarbon chain-containing group and at least one hydrolyzable
group are bonded to a silicon atom in the organosilicon compound
(A), where in at least one hydrolyzable group is bonded to a metal
atom in the metal compound (B), wherein a second hydrocarbon
chain-containing group having a length shorter than the length of
the first hydrocarbon chain-containing group may be bonded to the
metal atom in the metal compound (B), and wherein a molar ratio of
the metal compound B) to the organosilicon compound (A) as metal
compound (B)/organosilicon compound (A) is not less than 18 and not
more than 48.
Inventors: |
Shimazaki; Yasuharu (Osaka,
JP), Sakurai; Sayaka (Osaka, JP), Miyamoto;
Tomonori (Osaka, JP), Hozumi; Atsushi (Nagoya,
JP), Urata; Chihiro (Nagoya, JP) |
Applicant: |
Name |
City |
State |
Country |
Type |
SUMITOMO CHEMICAL COMPANY, LIMITED |
Tokyo |
N/A |
JP |
|
|
Assignee: |
SUMITOMO CHEMICAL COMPANY,
LIMITED (Tokyo, JP)
|
Family
ID: |
55857440 |
Appl.
No.: |
15/522,584 |
Filed: |
October 27, 2015 |
PCT
Filed: |
October 27, 2015 |
PCT No.: |
PCT/JP2015/080176 |
371(c)(1),(2),(4) Date: |
April 27, 2017 |
PCT
Pub. No.: |
WO2016/068103 |
PCT
Pub. Date: |
May 06, 2016 |
Prior Publication Data
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|
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Document
Identifier |
Publication Date |
|
US 20170313902 A1 |
Nov 2, 2017 |
|
Foreign Application Priority Data
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|
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Oct 31, 2014 [JP] |
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2014-223649 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C09D
5/00 (20130101); C09D 5/16 (20130101); C09D
7/61 (20180101); C09D 7/40 (20180101); C09D
7/20 (20180101); C09D 7/63 (20180101); C09D
183/14 (20130101); C09D 183/04 (20130101); C08G
77/58 (20130101) |
Current International
Class: |
C09D
5/00 (20060101); C09D 7/61 (20180101); C09D
183/14 (20060101); C09D 5/16 (20060101); C09D
7/40 (20180101); C09D 7/63 (20180101); C09D
183/04 (20060101); C09D 7/20 (20180101); C08G
77/58 (20060101) |
Field of
Search: |
;524/765 |
References Cited
[Referenced By]
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|
WO |
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|
Oct 2012 |
|
WO |
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Other References
Park et al., "Long Perfluoroalkyl Chains are not Required for
Dynamically Oleophobic Surfaces," Green Chemistry, vol. 15, 2013,
pp. 100-104. cited by applicant .
Urata et al., "How to Reduce Resistance to Movement of Alkane
Liquid Drops Across Tilted Surfaces Without Relying on Surface
Roughening and Perfluorination," Langmuir, vol. 28, Nov. 30, 2012,
pp. 17681-17689. cited by applicant .
Urata et al., "Smooth, Transparent and Nonperfluorinated Surfaces
Exhibiting Unusual Contact Angle Behavior Toward Organic Liquids,"
RSC Advances, vol. 2, 2012, pp. 9805-9808. cited by applicant .
Urata et al., "Unusual Dynamic Dewetting Behavior of Smooth
Perfluorinated Hybrid Films: Potential Advantages over Conventional
Textured and Liquid-Infused Perfluorinated Surfaces," Langmuir,
vol. 29, Sep. 11, 2013, pp. 12472-12482. cited by applicant .
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.
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tml, Mar. 13, 2012, 5 pages, with partial English translation.
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22, No. 14, 2006 (published online Jun. 3, 2006), pp. 6234-6237.
cited by applicant.
|
Primary Examiner: Egwim; Kelechi C
Attorney, Agent or Firm: Birch, Stewart, Kolasch &
Birch, LLP
Claims
The invention claimed is:
1. A water/oil-repellent coating composition comprising an
organosilicon compound (A), a metal compound (B), and a solvent
(C), wherein at least one first hydrocarbon chain-containing group
and at least one hydrolyzable group are bonded to a silicon atom in
the organosilicon compound (A), wherein at least one hydrolyzable
group is bonded to a metal atom in the metal compound (B), wherein
a second hydrocarbon chain-containing group having a length shorter
than the length of the first hydrocarbon chain-containing group may
be bonded to the metal atom in the metal compound (B), wherein the
first hydrocarbon chain-containing group is a hydrocarbon group,
wherein the hydrocarbon group has a carbon number of not less than
7 and not more than 17, wherein a molar ratio of the metal compound
(B) to the organosilicon compound (A) as metal compound
(B)/organosilicon compound (A) is not less than 18 and not more
than 48, and wherein the solvent (C) is methanol, ethanol,
propanol, or butanol.
2. The water/oil-repellent coating composition according to claim
1, wherein the molar ratio of the metal compound (B) to the
organosilicon compound (A) as metal compound (B)/organosilicon
compound (A) is not less than 18 and not more than 36.
3. The water/oil-repellent coating composition according to claim
1, wherein the organosilicon compound (A) is represented by formula
(I) below: ##STR00013## wherein R.sup.a represents the first
hydrocarbon group, each of A.sup.a1 independently represents a
hydrolyzable group, Z.sup.a1 represents the first hydrocarbon
chain-containing group, the second hydrocarbon chain-containing
group having a length shorter than a length of the first
hydrocarbon chain-containing group, or a hydrolyzable group,
R.sup.a and Z.sup.a1 may be the same or different when Z.sup.a1 is
the first hydrocarbon chain-containing group, Z.sup.a1 and A.sup.a1
may be the same or different when Z.sup.a1 is the hydrolyzable
group, and R.sup.a and Z.sup.a1 may be the same or different when
the water/oil-repellent coating composition comprises a plural
number of formulae (I).
4. The water/oil-repellent coating composition according to claim
1, wherein the metal compound (B) is represented by formula (II)
below: [Chemical Formula 2] M(R.sup.b1)(A.sup.b1).sub.m (II)
wherein R.sup.b1 represents the second hydrocarbon chain-containing
group or the hydrolyzable group, each of A.sup.b1 independently
represents a hydrolyzable group, M represents Al, Fe, In, Ge, Hf,
Si, Ti, Sn, Zr or Ta, and m represents an integer of 1 to 4
according to a kind of metal atom.
5. The water/oil-repellent coating composition according to claim
4, wherein R.sup.b1 and A.sup.b1 represent the same group in the
formula (II).
6. The water/oil-repellent coating composition according to claim
4, wherein M represents Si in the formula (II).
Description
TECHNICAL FIELD
The present invention relates to a water/oil-repellent coating
composition for forming a film capable of imparting water/oil
repellency to various kinds of substrates.
BACKGROUND ART
In various kinds of display devices, optical elements,
semiconductor elements, building materials, automobile components,
nanoimprint techniques and solar cell members, deposition of liquid
droplets on a surface of a substrate may cause a problem of
contamination and corrosion of the substrate, or further the
deterioration in the performance due to the contamination and
corrosion. Therefore, in these fields, the substrate surface is
required to have good water/oil repellency. Particularly, it is
required not only the prevention of deposition of liquid droplets
on the substrate surface, but also the ease of removing deposited
liquid droplets.
Patent Document 1 suggests a solution containing organosilane and a
metal alkoxide, and further containing an organic solvent, water
and a catalyst.
PRIOR ART DOCUMENTS
Patent Documents
Patent Document 1: JP 2013-213181 A
SUMMARY OF THE INVENTION
Problems to Be Solved By the Invention
The present inventors found that an organic-inorganic transparent
hybrid film obtained from the solution described in Cited Document
1 above may have insufficient hardness. When the hardness of a film
is insufficient, the film is apt to be broken by friction and
liquid droplets may become easily deposited or hardly removed,
which results in the problem of contamination and corrosion of a
substrate, or further deterioration in the performance. The object
of the present invention is to provide a water/oil-repellent
coating composition for forming a film capable of attaining both
water/oil repellency and abrasion resistance.
Solutions to the Problems
The present inventors extensively studied in view of the situations
described above, and resultantly found that when an organosilicon
compound in which a hydrocarbon chain-containing group and a
hydrolyzable group are bonded to a silicon atom and a metal
compound in which a hydrolyzable group is bonded to a metal atom
are used while the ratio of these compounds is adjusted within a
specific range, a water/oil-repellent coating composition capable
of providing a coating film having both water/oil repellency and
abrasion resistance is obtained, thereby leading to the completion
of the present invention.
The water/oil-repellent coating composition of the present
invention comprises an organosilicon compound (A) and a metal
compound (B),
wherein at least one first hydrocarbon chain-containing group and
at least one hydrolyzable group are bonded to a silicon atom in the
organosilicon compound (A),
wherein at least one hydrolyzable group is bonded to a metal atom
in the metal compound (B),
wherein a second hydrocarbon chain-containing group having a length
shorter than the length of the first hydrocarbon chain-containing
group may be bonded to the metal atom in the metal compound B),
and
wherein a molar ratio of the metal compound (B) to the
organosilicon compound (A) as metal compound (B)/organosilicon
compound A) is not less than 18 and not more than 48.
The water/oil-repellent coating composition has preferably the
molar ratio of the metal compound (B) to the organosilicon compound
(A) as metal compound (B)/organosilicon compound (A) is not less
than 18 and not more than 36.
The water/oil-repellent coating composition preferably further
comprises a solvent (C). The solvent (C) preferably includes an
alcohol-based solvent.
The organosilicon compound (A) is preferably represented by formula
(I) below:
##STR00001##
wherein R.sup.a represents the first hydrocarbon group,
each of A.sup.a1 independently represents a hydrolyzable group,
Z.sup.a1 represents the first hydrocarbon chain-containing group,
the second hydrocarbon chain-containing group having a length
shorter than a length of the first hydrocarbon chain-containing
group, or a hydrolyzable group,
R.sup.a and Z.sup.a1 may be the same or different when Z.sup.a1 is
the first hydrocarbon chain-containing group,
Z.sup.a1 and A.sup.a1 may be the same or different when Z.sup.a1 is
the hydrolyzable group, and
R.sup.a and Z.sup.a1 may be the same or different when the
water/oil-repellent coating composition comprises a plural number
of formulae (I).
The metal compound (B) is preferably represented by formula (II)
below: M(R.sup.b1)(A.sup.b1) (II)
wherein R.sup.b1 represents the second hydrocarbon group or the
hydrolyzable group,
each of A.sup.b1 independently represents a hydrolyzable group,
M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr or Ta, and
m represents an integer of 1 to 4 according to a kind of metal
atom.
In the formula (II), R.sup.b1 and A.sup.b1 preferably represent the
same group and M preferably represents Si in the formula (II).
Effects of the Invention
A water/oil-repellent coating composition of the present invention
comprises an organosilicon compound in which a hydrocarbon
chain-containing group and a hydrolyzable group are bonded to a
silicon atom and a metal compound in which a hydrolyzable group is
bonded to a metal atom, and the molar ratio of these compounds is
adjusted within a specific range, and therefore both of the
water/oil repellency and abrasion resistance can be attained.
Mode for Carrying Out the Invention
A water/oil-repellent coating composition of the present invention
comprises an organosilicon compound (A) and a metal compound (B),
wherein at least one first hydrocarbon chain-containing group and
at least one hydrolyzable group are bonded to a silicon atom in the
organosilicon compound (A), wherein at least one hydrolyzable group
is bonded to a metal atom in the metal compound (B), and wherein a
second hydrocarbon chain-containing group having a hydrocarbon
chain moiety with a carbon number smaller than that of the first
hydrocarbon chain-containing group may be bonded to the metal atom.
The hydrolyzable group bonded to the silicon atom or metal atom in
the water/oil-repellent coating composition is subjected to
hydrolysis and polycondensation to form a coating film where the
first hydrocarbon chain-containing group is bonded to a part of
silicon atoms forming the coating film. The first hydrocarbon
chain-containing group imparts a water/oil repellency function to
the coating film, and an element (e.g. the above-mentioned metal
atom), to which the first hydrocarbon chain-containing group is not
bonded, functions substantially as a spacer in the coating film. In
the water/oil-repellent coating composition of the present
invention, the molar ratio of the organosilicon compound (A) and
the metal compound (B) is adjusted within a specific range, and
thereby the first hydrocarbon chain-containing group and the spacer
exist at a specific ratio in the resulting coating film. Thus, a
coating film can be provided having an improved water/oil
repellency function and excellent abrasion resistance.
In the organosilicon compound (A), the first hydrocarbon
chain-containing group bonded to the center silicon atom is a
monovalent group containing a hydrocarbon chain, and the
hydrocarbon chain imparts water/oil repellency to the interface as
surface of the resulting coating film. Particularly, a friction
coefficient between a liquid droplet, as water droplet, oil droplet
or the like, and the coating film decreases, and thus the liquid
droplet moves more easily.
The first hydrocarbon chain-containing group is composed only of a
hydrocarbon group (hydrocarbon chain), and a part of methylene
groups (--CH.sub.2--) of the hydrocarbon chain may be replaced by
oxygen atoms as necessary. Even the group in which a part of itself
is replaced by oxygen atoms as described above is classified as a
hydrocarbon chain-containing group because a hydrocarbon chain
exists in the remaining part. Methylene groups (--CH.sub.2--)
adjacent to Si atoms are not replaced by oxygen atoms, and two
continuous methylene groups (--CH.sub.2--) are not simultaneously
replaced by oxygen atoms. Hereinafter, the first hydrocarbon
chain-containing group is described and an oxygen-unsubstituted
hydrocarbon chain-containing group (i.e., monovalent hydrocarbon
group) is taken as an example unless otherwise specified, and a
part of the methylene groups (--CH.sub.2--) can be replaced by
oxygen atoms in the following.
The first hydrocarbon chain-containing group has a carbon number of
preferably not less than 6 and not more than 20, more preferably
not less than 7 and not more than 17, further preferably not less
than 8 and not more than 15 in the case where the first hydrocarbon
chain-containing group is a hydrocarbon group.
The first hydrocarbon chain-containing group may be a branched
chain or a linear chain in the case of a hydrocarbon group. The
first hydrocarbon chain-containing group is preferably a saturated
or unsaturated aliphatic hydrocarbon chain-containing group, more
preferably a saturated aliphatic hydrocarbon chain-containing group
in the case of a hydrocarbon group.
The saturated aliphatic hydrocarbon chain-containing group is more
preferably a saturated aliphatic hydrocarbon group. Examples of the
saturated aliphatic hydrocarbon group include hexyl group, heptyl
group, octyl group, nonyl group, decyl group, undecyl group,
dodecyl group, tridecyl group, tetradecyl group, pentadecyl group,
hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group
and icosyl group in the case of a hydrocarbon group.
When a part of methylene groups (--CH.sub.2--) of the hydrocarbon
group are replaced by oxygen atoms, the hydrocarbon group is
preferably a saturated aliphatic hydrocarbon group. Specific
examples of the group in which a part of methylene groups
(--CH.sub.2--) of the hydrocarbon group are replaced by oxygen
atoms may include groups having (poly)ethylene glycol units and
groups having (poly)propylene glycol units.
In the organosilicon compound (A), the number of first the
hydrocarbon chain-containing groups bonded to the center silicon
atom is preferably not less than 1 and not more than 2, especially
preferably 1.
The hydrolyzable group of the organosilicon compound (A) may be a
group that provides a hydroxy group (silanol group) through
hydrolysis, and preferred examples thereof may include alkoxy
groups with a carbon number of 1 to 4, such as methoxy group,
ethoxy group, propoxy group and butoxy group; hydroxy group;
acetoxy group; chlorine atom; and isocyanate group. In particular,
alkoxy groups with a carbon number of 1 to 4 are preferable, and
alkoxy groups with a carbon number of 1 or 2 are more
preferable.
In the organosilicon compound (A), the number of hydrolyzable
groups bonded to the center silicon atom is normally not less than
1, preferably not less than 2, and is normally preferably not more
than 3.
In addition to the first hydrocarbon chain-containing group and
hydrolyzable group, the second hydrocarbon chain-containing group
that comprises a hydrocarbon chain moiety with a carbon number
smaller than that of the first hydrocarbon group-containing group
may be bonded to the silicon atom of the organosilicon compound
(A).
The second hydrocarbon chain-containing group should have a length
shorter than that of the first hydrocarbon chain-containing group.
The length of each of the first and second hydrocarbon
chain-containing groups can be evaluated as a length (longest chain
length) of the longest linear chain (hereinafter, also referred to
as a "main chain") including elements that is bonded to metal atoms
such as Si atoms in the hydrocarbon chain-containing group. For
ensuring that the second hydrocarbon chain-containing group has a
main chain shorter than that of the first hydrocarbon
chain-containing group, for example, the carbon number of the
hydrocarbon chain moiety in the second hydrocarbon chain-containing
group is preferably smaller than the carbon number of the first
hydrocarbon chain moiety. Normally, the second hydrocarbon
chain-containing group is composed only of a hydrocarbon group
(hydrocarbon chain) as in the case of the first hydrocarbon
chain-containing group, and may be a group in which a part of
methylene groups (--CH.sub.2--) are replaced by oxygen atoms.
Methylene groups (--CH.sub.2--) adjacent to Si atoms are not
replaced by oxygen atoms, and two continuous methylene groups
(--CH.sub.2--) are not simultaneously replaced by oxygen atoms.
The carbon number of the hydrocarbon chain moiety means the number
of carbon atoms that form the hydrocarbon group (hydrocarbon chain)
in the case of an oxygen-unsubstituted hydrocarbon chain-containing
group, while the carbon number of the hydrocarbon chain moiety
means the number of carbon atoms which number is counted with the
assumption that the oxygen atoms are considered as methylene groups
(--CH.sub.2--) in the case of an oxygen-substituted hydrocarbon
chain-containing group.
Hereinafter, the second hydrocarbon chain-containing group is
described while an oxygen-unsubstituted hydrocarbon
chain-containing group (i.e., monovalent hydrocarbon group) is
taken as an example unless otherwise specified, and a part of the
methylene groups (--CH.sub.2--) can be replaced by oxygen atoms in
the following.
The second hydrocarbon chain-containing group has a carbon number
of preferably not less than 1 and not more than 5, more preferably
not less than 1 and not more than 3 in the case where the second
hydrocarbon chain-containing group is a hydrocarbon group. The
second hydrocarbon chain-containing group may be a branched chain
or a linear chain in the case of a hydrocarbon group.
The second hydrocarbon chain-containing group is preferably a
saturated or unsaturated aliphatic hydrocarbon chain-containing
group, more preferably a saturated aliphatic hydrocarbon
chain-containing group in the case of a hydrocarbon group. The
saturated aliphatic hydrocarbon chain-containing group is more
preferably a saturated aliphatic hydrocarbon group in the case of a
hydrocarbon group. Examples of the saturated aliphatic hydrocarbon
group include methyl group, ethyl group, propyl group, butyl group
and pentyl group.
When a part of methylene groups (--CH.sub.2--) of the hydrocarbon
group are replaced by oxygen atoms, the hydrocarbon group is
preferably a saturated aliphatic hydrocarbon group, and specific
examples of the group in which a part of methylene groups
(--CH.sub.2--) of the hydrocarbon group are replaced by oxygen
atoms may include groups having (poly)ethylene glycol units.
In the organosilicon compound (A), the number of the second
hydrocarbon chain-containing groups bonded to the center silicon
atom is preferably not more than 2, more preferably not more than
1, especially preferably 0.
Specifically, the organosilicon compound (A) is preferably a
compound represented by the following formula (I).
##STR00002##
wherein R.sup.a represents the first hydrocarbon chain-containing
group,
each of A.sup.a1 independently represents a hydrolyzable group,
Z.sup.a1 represents the first hydrocarbon chain-containing group,
the second hydrocarbon chain-containing group or the hydrolyzable
group,
R.sup.a and Z.sup.a1 may be the same or different when Z.sup.a1 is
the first hydrocarbon chain-containing group,
Z.sup.a1 and A.sup.a1 may be the same or different when Z.sup.a1 is
a hydrolyzable group, and
R.sup.a and Z.sup.a1 may be the same or different when the
transparent film comprises a plural number of formulae (I).
In the formula (I), the first hydrocarbon chain-containing group
represented by R.sup.a or Z.sup.a1, the second hydrocarbon
chain-containing group represented by Z.sup.a1, and the
hydrolyzable group represented by A.sup.a1 or Z.sup.a1 can be
appropriately selected from the groups described above as the first
hydrocarbon chain-containing group, the second hydrocarbon
chain-containing group and the hydrolyzable group,
respectively.
In the formula (I), Z.sup.a1 is preferably the second hydrocarbon
chain-containing group or the hydrolyzable group, more preferably
the hydrolyzable group.
Preferable examples of the organosilicon compound (A) may include
compounds having one first hydrocarbon chain-containing group and
three hydrolyzable groups; and compounds having one first
hydrocarbon chain-containing group, one second hydrocarbon
chain-containing group and two hydrolyzable groups.
In the compound having one first hydrocarbon chain-containing group
and three hydrolyzable groups, the three hydrolyzable group s are
bonded to the silicon atom. Examples of the group in which three
hydrolyzable groups are bonded to a silicon atom include
trialkoxysilyl groups such as trimethoxysilyl group, triethoxysilyl
group, tripropoxysilyl group and tributoxysilyl group;
trihydroxysilyl group; triacetoxysilyl group; trichlorosilyl group;
and triisocyanatesilyl group, and examples of the compound having
one first hydrocarbon chain-containing group and three hydrolyzable
groups include compounds in which one first hydrocarbon
chain-containing group selected from the groups described above is
bonded to the silicon atom of the above-mentioned group in which
three hydrolyzable groups are bonded to a silicon atom.
In the compound having one first hydrocarbon chain-containing
group, one second hydrocarbon chain-containing group and two
hydrolyzable groups, one second hydrocarbon chain-containing group
and two hydrolyzable groups are bonded to a silicon atom. Examples
of the group in which one second hydrocarbon chain-containing group
and two hydrolyzable groups are bonded to a silicon atom include
alkyldialkoxysilyl groups such as methyldimethoxysilyl group,
ethyldimethoxysilyl group, methyldiethoxysilyl group,
ethyldiethoxysilyl group and methyldipropoxysilyl group, and
examples of the compound having one first hydrocarbon
chain-containing group, one second hydrocarbon chain-containing
group and two hydrolyzable groups include compounds in which one
first hydrocarbon chain-containing group selected from the groups
described above is bonded to the silicon atom of the
above-mentioned group.
Specific examples of the compound having one first hydrocarbon
chain-containing group and three hydrolyzable groups include
alkyltrialkoxysilanes having an alkyl group with a carbon number of
6 to 20 such as alkyltrimethoxysilanes having an alkyl group with a
carbon number of 6 to 20, and alkyltriethoxysilanes having an alkyl
group with a carbon number of 6 to 20; alkyltrihydroxysilanes
having an alkyl group with a carbon number of 6 to 20;
alkyltriacetoxysilanes having an alkyl group with a carbon number
of 6 to 20; alkyltrichlorosilanes having an alkyl group with a
carbon number of 6 to 20; and alkyltriisocyanatesilanes having an
alkyl group with a carbon number of 6 to 20.
Specific examples of the compound having one first hydrocarbon
chain-containing group, one second hydrocarbon chain-containing
group and two hydrolyzable groups include
alkylmethyldialkoxysilanes such as alkylmethyldimethoxysilanes
having an alkyl group with a carbon number of 6 to 20, and
alkylmethyldiethoxysilanes having an alkyl group with a carbon
number of 6 to 20; alkylmethyldihydroxysilanes having an alkyl
group with a carbon number of 6 to 20; alkylmethyldiacetoxysilanes
having an alkyl group with a carbon number of 6 to 20,
alkylmethyldichlorosilanes having an alkyl group with a carbon
number of 6 to 20; and alkylmethyldiisocyanatesilanes having an
alkyl group with a carbon number of 6 to 20.
In particular, compounds having one first hydrocarbon
chain-containing group and three hydrolyzable groups are
preferable, and alkyltrialkoxysilanes are more preferable.
The metal compound (B) contained in the water/oil-repellent coating
composition together with the organosilicon compound (A) is a metal
compound in which at least one hydrolyzable group is bonded to the
center metal atom. The second hydrocarbon chain-containing group
may be bonded to the metal atom. The length of the longest chain in
the second hydrocarbon chain-containing group is shorter than the
length of the longest chain in the first hydrocarbon
chain-containing group bonded to the center silicon atom of the
organosilicon compound (A), and the length of the longest chain in
the metal compound (B) is shorter than the length of the longest
chain in the organosilicon compound. Accordingly, a structure
derived from the metal compound (B) is not bulky than a structure
derived from the organosilicon compound (A). Thus a part having a
spacer function can be formed in the resulting coating film due to
the metal compound B) contained in the water/oil-repellent coating
composition.
The center metal atom in the metal compound (B) may be a metal atom
that is capable of forming a metal alkoxide with a bond to an
alkoxy group, and the metals here include semimetals such as Si and
Ge. Specific examples of the center metal atom in the metal
compound (B) include trivalent metals such as Al, Fe and In;
tetravalent metals such as Ge, Hf, Si, Ti, Sn and Zr; and
pentavalent metals such as Ta. The center metal atom is preferably
a trivalent metal such as Al; a tetravalent metal such as Si, Ti,
Zr or Sn; more preferably Al, Si, Ti or Zr; further preferably
Si.
The hydrolyzable group in the metal compound (B) may be a group
similar to the hydrolyzable group in the organosilicon compound
(A), and is preferably an alkoxy group with a carbon number of 1 to
4, more preferably an alkoxy group with a carbon number of 1 or 2.
The hydrolyzable groups in the organosilicon compound (A) and the
metal compound (B) may be the same or different. Each of the
hydrolyzable groups in the organosilicon compound (A) and the metal
compound (B) is preferably an alkoxy group with a carbon number of
1 to 4.
In the metal compound (B), the number of hydrolyzable groups is
preferably not less than 1, more preferably not less than 2,
further preferably not less than 3, and is preferably not more than
4.
The second hydrocarbon chain-containing group in the metal compound
(B) can be appropriately selected from the groups described above,
and the number is preferably not more than 1, especially preferably
0.
Specifically, the metal compound (B) is preferably a compound
represented by the following formula (II).
M(R.sup.b1)(A.sup.b1).sub.m (II)
wherein R.sup.b1 represents the second hydrocarbon group or the
hydrolyzable group,
A.sup.b1 represents a hydrolyzable group,
M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr or Ta, and m
represents an integer of 1 to 4 according to a kind of metal
atom.
In the formula (II), the second hydrocarbon chain-containing group
represented by R.sup.b1, and the hydrolyzable group represented by
R.sup.b1 or A.sup.b1 can be appropriately selected from the groups
described above as the second hydrocarbon chain-containing group
and the hydrolyzable group.
In the formula (II), R.sup.b1 is preferably a hydrolyzable group.
When R.sup.b1 is a hydrolyzable group, R.sup.b1 and A.sup.b1 may be
the same or different, and is preferably the same. Further, the
hydrolyzable groups in the organosilicon compound (A) and the metal
compound (B) may be the same or different.
In the formula (II), M is preferably Al, Si, Ti, Zr or Sn, more
preferably Al, Si, Ti or Zr, further preferably Si. The alkoxide of
such a metal atom is easily liquefied, so that the uniformity of
the distribution of the following structure (b) capable of
functioning as a spacer in the coating film is easily improved.
In the formula (II), m represents 2 when M is a trivalent metal
such as Al, Fe or In, m represents 3 when M is a tetravalent metal
such as Ge, Hf, Si, Ti, Sn or Zr, and m represents 4 when M is a
pentavalent metal such as Ta.
Preferable examples of the metal compound (B) may include compounds
having only the hydrolyzable group; and compounds having one second
hydrocarbon chain-containing group and two hydrolyzable groups.
Examples of the compound having only the hydrolyzable group include
tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane,
tetrapropoxysilane and tetrabutoxysilane; trialkoxyaluminums such
as triethoxyaluminum, tripropoxyaluminum and tributoxyaluminum;
trialkoxyirons such as triethoxyiron; trialkoxyindiums such as
trimethoxyindium, triethoxyindium, tripropoxyindium and
tributoxyindium; tetraalkoxygermaniums such as
tetramethoxygermanium, tetraethoxygermanium, tetrapropoxygermanium
and tetrabutoxygermanium; tetraalkoxyhafniums such as
tetramethoxyhafnium, tetraethoxyhafnium, tetrapropoxyhafnium and
tetrabutoxyhafnium; tetraalkoxytitaniums such as
tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium and
tetrabutoxytitanium; tetraalkoxytins such as tetramethoxytin,
tetraethoxytin, tetrapropoxytin and tetrabutoxytin;
tetraalkoxyzirconiums such as tetramethoxyzirconium,
tetraethoxyzirconium, tetrapropoxyzirconium and
tetrabutoxyzirconium; and pentaalkoxytantalums such as
pentamethoxytantalum, pentaethoxytantalum, pentapropoxytantalum and
pentabutoxytantalum.
Examples of the compound having the second hydrocarbon
chain-containing group and the hydrolyzable group include
alkyltrialkoxysilanes such as methyltrimethoxysilane,
ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane
and methyltripropoxysilane; and alkenyltrialkoxysilanes such as
vinyltrimethoxysilane and vinyltriethoxysilane.
The water/oil-repellent coating composition of the present
invention contains the organosilicon compound (A) and the metal
compound (B) at a specific ratio, and thus a coating film can be
provided which exhibits an improved water/oil repellency function,
and excellent hardness. Specifically, in the water/oil-repellent
coating composition of the present invention, the molar ratio of
the metal compound (B) to the organosilicon compound (A) as metal
compound (B)/organosilicon compound (A) is not less than 18 and not
more than 48, and is preferably not more than 44, more preferably
not more than 40, further preferably not more than 36.
The water/oil-repellent coating composition of the present
invention may further contain a solvent (C) in addition to the
organ osilicon compound (A) and the metal compound (B). Examples of
the solvent (C) include an alcohol-based solvent, an ether-based
solvent, a ketone-based solvent, an ester-based solvent and an
amide-based solvent. These solvents may be used singly, or used in
combination of two or more thereof.
Examples of the alcohol-based solvent include methanol, ethanol,
propanol, butanol, ethylene glycol, propylene glycol and diethylene
glycol, examples of the ether-based solvent include dimethoxy
ethane, tetrahydrofuran and dioxane, examples of the ketone-based
solvent include acetone and methyl ethyl ketone, examples of the
ester-based solvent include ethyl acetate and butyl acetate, and
examples of the amide-based solvent include dimethylformamide.
In particular, alcohol-based solvents and ether-based solvents are
preferable, and alcohol-based solvents are more preferable.
The amount of the solvent (C) is preferably not more than 120 parts
by mass, more preferably not more than 80 parts by mass, further
preferably not more than 60 parts by mass, especially preferably
not more than 40 parts by mass, and preferably not less than 3
parts by mass, more preferably not less than 5 parts by mass,
further preferably not less than 10 parts by mass, especially
preferably not less than 20 parts by mass based on 1 part by mass
of the total of the organosilicon compound (A) and the metal
compound (B).
Further, in the water/oil-repellent coating composition of the
present invention, a catalyst may coexist as necessary. The
catalyst can be arbitrarily selected from acidic compounds such as
hydrochloric acid; basic compounds; organometallic compounds and
the like, which are generally used in a sol-gel method. Examples of
the catalyst include acid compounds; basic compounds; and
organometallic compounds. Examples of the acidic compound include
inorganic acids such as hydrochloric acid and nitric acid; and
organic acids such as acetic acid. Examples of the basic compound
include ammonia and amine. The organometallic compound include an
organometallic compound having as a center metal a metal element
such as Al, Fe, Zn, Sn or Zr, and examples thereof include
organoaluminum compounds such as aluminum-acetylacetone complexes
and aluminum-ethyl acetoacetate complexes; organoiron compounds
such as iron octylate; organozinc compounds such as zinc
acetylacetonate monohydrate, zinc naphthenate and zinc octylate;
and organotin compounds such as dibutyl tin diacetate
complexes.
In particular, the catalyst is preferably an organometallic
compound, more preferably an organoaluminum compound, especially
preferably an organoaluminum ethyl acetoacetate compound.
The amount of the catalyst is preferably not less than 0.0001 parts
by mass, more preferably not less than 0.1 parts by mass, further
preferably not less than 0.5 parts by mass, especially preferably
not less than 1 part by mass, and preferably not more than 20 parts
by mass, more preferably not more than 10 parts by mass, further
preferably not more than 5 parts by mass based on 100 parts by mass
of the total of the organosilicon compound (a) and the metal
compound (b).
When the catalyst is an acidic compound (especially preferably
hydrochloric acid), the amount of the acidic compound is preferably
not less than 0.0001 parts by mass, more preferably not less than
0.0005 parts by mass, further preferably not less than 0.001 parts
by mass, and preferably not more than 1 part by mass, more
preferably not more than 0.5 parts by mass, further preferably not
more than 0.3 parts by mass based on 100 parts by mass of the total
of the organosilicon compound (A) and the metal compound (B).
Further, at the contact of the organosilicon compound (A) and the
metal compound (B) to a substrate, various kinds of additives such
as an antioxidant, a rust inhibitor, an ultraviolet absorber, a
light stabilizer, an antifungal agent, an antibacterial agent, an
organism deposition preventing agent, a deodorizer, a pigment, a
flame retardant and an antistatic agent may coexist.
Examples of the antioxidant include phenol-based antioxidants,
sulfur-based antioxidants, phosphorus-based antioxidants and
hindered amine-based antioxidants.
Examples of the phenol-based antioxidant include
n-octadecyl-3-(4-hydroxy-3,5-di-t-butylphenyl)propionate,
2,6-di-t-butyl-4-methylphenol,
2,2-thio-diethylene-bis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],
tri-ethyleneglycol-bis-[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate]-
,
3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimet-
hylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane,
tetrakis{3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionic
acid}pentaerythrityl esters,
2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl
acrylate,
2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenyl
acrylate,
1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benze-
ne, tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate,
1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(-
1H,3H,5H)-trione, 2,2'-methylenebis(6-t-butyl-4-methylphenol),
4,4'-butylidenebis(6-t-butyl-3-methylphenol) and
4,4'-thiobis(6-t-butyl-3-methylphenol).
Examples of the sulfur-based antioxidant include
3,3'-thiodipropionic acid di-n-dodecyl esters, 3,3'-thiodipropionic
acid di-n-tetradecyl esters, 3,3'-thiodipropionic acid
di-n-octadecyl esters and tetrakis(3-dodecylthiopropionic
acid)pentaerythritol esters.
Examples of the phosphorus-based antioxidant include
tris(2,4-di-t-butylphenyl)phosphite,
bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite,
bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite,
bis(2,4-di-cumylphenyl)pentaerythritol diphosphite,
tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylene diphosphonite and
bis-[2,4-di-t-butyl-(6-methyl)phenyl]ethyl phosphite.
Examples of the hindered amine-based antioxidant include sebacic
acid bis(2,2,6,6-tetramethyl-4-piperidyl)esters (melting point: 81
to 86.degree. C.), 2,2,6,6-tetramethyl-4-piperidyl methacrylate
(melting point: 58.degree. C.), and
poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-
-tetramethyl-4-piperidyl)imino}-1,6-hexamethylene{(2,2,6,6-tetramethyl-4-p-
iperidyl)imino}].
Examples of the rust inhibitor include alkanol amines such as
triethanol amine; quaternary ammonium salts; alkanethiols; azoles
such as imidazoline, imidazole, alkylimidazoline derivatives,
benzimidazole, 2-mercaptobenzimidazole and benzotriazole; sodium
metavanadate; bismuth citrate; phenol derivatives; amine compounds
such as aliphatic amines including alkylamines and
polyalkenylamines, aromatic amines, ethoxylated amines,
cyanoalkylamines, cyclohexylamine benzoate, aliphatic diamines such
as alkylenediamines, and aromatic diamines; amides of the amine
compounds and carboxylic acid; alkyl esters; pyrimidine; naphthenic
acid; sulfonic acid composites; nitrous acid salts such as calcium
nitrite, sodium nitrite and dicyclohexylamine nitrite; polyol
compounds such as polyalcohols and polyphenols; heteropolyacid
salts such as sodium molybdate, sodium tungstate, sodium
phosphonate, sodium chromate and sodium silicate; gelatin; polymers
of carboxylic acid; nitro compounds; formaldehyde; acetylene
alcohol; thiol compounds such as aliphatic thiols, aromatic thiols
and acetylene thiols; sulfide compounds such as aliphatic sulfide,
aromatic sulfide and acetylene sulfide; sulfoxide compounds such as
sulfoxide and dibenzylsulfoxide; thio urea; combinations of an
amine or quaternary ammonium salt and halogen ions; combinations of
an alkylamine and potassium iodide; combinations of tannin and
sodium phosphate; combinations of triethanolamine and
laurylsarcosine; combinations of triethanolamine, laurylsarcosine
and benzotriazole; and combinations of an alkylamine,
benzotriazole, sodium nitrite and sodium phosphate.
Examples of the ultraviolet absorber/light stabilizer include for
example 2-(5-methyl-2-hydroxyphenyl)benzotriazole,
2-[2-hydroxy-3,5-bis(.alpha.,.alpha.-dimethylbenzyl)phenyl]-2H-benzotriaz-
ole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole,
2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, condensation products
of
methyl-3-[3-t-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate-p-
olyethylene glycol (molecular weight: about 300), hydroxyphenyl
benzotriazole derivatives,
2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5[(hexyl)oxy]-phenol and
2-ethoxy-2'-ethyl-oxalic acid bisanilide.
Examples of the antifungal agent/antibacterial agent include
2-(4-thiazolyl)benzimidazole, sorbic acid,
1,2-benzisothiazolin-3-one, (2-pyridylthio-1-oxide)sodium,
dehydroacetic acid, 2-methyl-5-chloro-4-isothiazolone complexes,
2,4,5,6-tetrachlorophthalonitrile, methyl 2-benzimidazolecarbamate,
methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate, mono- or
dibromocyanoacetamides, 1,2-dibromo-2,4-dicyanobutane,
1,1-dibromo-1-nitropropanol and
1,1-dibromo-1-nitro-2-acetoxypropane.
Examples of the organism deposition preventing agent include
tetramethylthiuram disulfide, zinc
bis(N,N-dimethyldithiocarbamate),
3-(3,4-dichlorophenyl)-1,1-dimethylurea, dichloro-N-((dimethyl
amino)sulfonyl)fluoro-N-(P-tryl)methanesulpheneamide, pyridine-tri
phenylborane,
N,N-dimethyl-N'-phenyl-N'-(fluorodichloromethylthio)sulfamide,
cuprous thiocyanate (1), cuprous oxide, tetrabutylthiuram
disulfide, 2,4,5,6-tetrachloroisophthalonitrile, zinc
ethylenebisdithiocarbamate,
2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine,
N-(2,4,6-trichlorophenyl)maleimide,
bis(2-pyridinethiol-1-oxide)zinc salts,
bis(2-pyridinethiol-1-oxide)copper salts,
2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine,
4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, furanones,
alkylpyridine compounds, gramine-based compounds and isotonyl
compounds.
Examples of the deodorizer include organic acids such as lactic
acid, succinic acid, malic acid, citric acid, maleic acid, malonic
acid, ethylenediamine polyacetic acid, alkane-1,2-dicarboxylic
acids, alkene-1,2-dicarboxylic acids, cycloalkane-1,2-dicarboxylic
acids, cycloalkene-1,2-dicarboxylic acids and naphthalene sulfonic
acid; fatty acid metals such as zinc undecylenate, zinc 2-ethyl
hexanoate and zinc ricinoleate; metal compounds such as iron oxide,
iron sulfate, zinc oxide, zinc sulfate, zinc chloride, silver
oxide, copper oxide, metal (iron, copper or the like) chlorophyllin
sodium, metal (iron, copper, cobalt or the like) phthalocyanine,
metal (iron, copper, cobalt or the like) tetrasulfonic acid
phthalocyanine, titanium dioxide and visible light-responsive
titanium dioxide nitrogen-doped-type or the like); cyclodextrins
such as .alpha.-, .beta.- or .gamma.-cyclodextrin, methyl
derivatives thereof, hydroxypropyl derivatives, glucosyl
derivatives and maltosyl derivatives; and porous materials such as
acrylic acid-based polymers including porous methacrylic acid
polymers and porous acrylic acid polymers, aromatic-based polymers
including porous divinylbenzene polymers, porous
styrene-divinylbenzene-vinylpyridine polymers and porous
divinylbenzene-vinylpyridine polymers, copolymers thereof, chitin,
chitosan, activated carbon, silica gel, activated alumina, zeolite
and ceramics.
Examples of the pigment include carbon black, titanium oxide,
phthalocyanine-based pigments, quinacridone-based pigments,
isoindolinone-based pigments, perylene or perynine-based pigments,
quinophthalone-based pigments, diketopyrrolo-pyrrole-based
pigments, dioxazine-based pigments, disazo-condensed-based pigments
and benzimidazolone-based pigments.
Examples of the flame retardant include decabromobiphenyl, antimony
trioxide, phosphorus-based flame retardants and aluminum
hydroxide.
Examples of the antistatic agent include cationic surfactants of
quaternary ammonium salt type; amphoteric surfactants of betaine
type; anionic surfactants of alkyl phosphate type; cationic
surfactants such as primary amine salts, secondary amine salts,
tertiary amine salts, quaternary amine salts and pyridine
derivatives; anionic surfactants such as sulfated oil, soap,
sulfated ester oil, sulfated amide oil, sulfated ester salts of
olefins, fatty alcohol sulfuric acid ester salts, alkylsulfuric
acid ester salts, fatty acid ethyl sulfonic acid salts,
alkylnaphthalene sulfonic acid salts, alkylbenzene sulfonic acid
salts, succinic acid ester sulfonic acid salts and phosphoric acid
ester salts; nonionic surfactants such as partial fatty acid esters
of polyhydric alcohols, ethylene oxide adducts of fatty alcohols,
ethylene oxide adducts of fatty acids, ethylene oxide adducts of
fatty amino or fatty acid amides, ethylene oxide adducts of
alkylphenols, ethylene oxide adducts of partial fatty acid esters
of polyhydric alcohols and polyethylene glycol; and amphoteric
surfactants such as carboxylic acid derivatives and imidazoline
derivatives.
As additives, a lubricant, a filler, a plasticizer, a nucleating
agent, an antiblocking agent, a foaming agent, an emulsifier, a
brightening agent, a binder and the like may further coexist.
When these additives are contained, the content of the additives is
normally 0.1 to 70% by mass, preferably 0.1 to 50% by mass, more
preferably 0.5 to 30% by mass, further preferably 2 to 15% by mass
in the coating composition containing the organosilicon compound
(A) and the metal compound (B).
The content of the total of the organosilicon compound (A) and the
metal compound (B) (the total of the organosilicon compound A), the
metal compound (B) and the solvent (C) when the solvent (C) is
contained) is normally not less than 60% by mass, preferably not
less than 75% by mass, more preferably not less than 85% by mass,
further preferably not less than 95% by mass in the
water/oil-repellent coating composition.
Further, the water/oil-repellent coating composition of the present
invention includes the organosilicon compound (A) in which one
first hydrocarbon chain-containing group with a carbon number of
not less than 7 and not more than 9 (especially 8) and three
hydrolyzable groups are bonded to a silicon atom, and the metal
compound (B) in which four hydrolyzable groups are bonded to a
metal atom (especially a silicon atom), and the weight ratio of the
metal compound (B) to the organosilicon compound (A) as metal
compound (B)/organosilicon compound (A) is especially preferably
not less than 18 and not more than 36. When the structure and molar
ratio of the organosilicon compound (A) to the metal compound (B)
are adjusted as described above, the resulting coating film attains
both hardness and water/oil repellency to a higher degree.
By contacting the water/oil-repellent coating composition of the
present invention to a substrate, the hydrolyzable groups of the
organosilicon compound (A) and the metal compound (B) are subjected
to hydrolysis and polycondensation to form a water/oil-repellent
coating film on the surface of the substrate.
The method for contacting the water/oil-repellent coating
composition to a substrate is preferably a method in which a
surface of the substrate is coated with the water/oil-repellent
coating composition for example. Examples of the coating method
include a spin coating method, a dip coating method, a spray
coating method, a roll coating method, a bar coating method and a
die coating method, and a spin coating method or spray coating
method is preferable.
The water/oil-repellent coating composition and the substrate are
preferably left standing in air while being in contact with each
other, and moisture in the air is whereby captured to accelerate
hydrolysis and polycondensation of the hydrolyzable group. The
resulting coating film may be further dried. The heating/drying
temperature is normally 40 to 250.degree. C., preferably 60 to
200.degree. C., further preferably 60 to 150.degree. C.
The resulting water/oil-repellent coating film comprises a
network-like backbone in which silicon atoms and the metal atoms
(preferably only silicon atoms) are bonded via oxygen atoms. The
water/oil-repellent coating film comprises a structure in which the
first hydrocarbon chain-containing group is bonded to a part of
silicon atoms originating from the organosilicon compound (A) and
forming the backbone.
The structure in which the first hydrocarbon chain-containing group
is bonded to a silicon atom is preferably a structure (a)
represented by the following formula (1).
##STR00003##
wherein R.sup.a represents the first hydrocarbon chain-containing
group,
Z.sup.a2 represents the first hydrocarbon chain-containing group,
the second hydrocarbon chain-containing group or --O-- group,
R.sup.a and Z.sup.a2 may be the same or different when Z.sup.a2 is
the first hydrocarbon chain-containing group, and
R.sup.a and Z.sup.a2 may be the same or different when the
transparent film comprises a plural number of formulae (1).
In the formula (1), the first hydrocarbon chain-containing group
represented by R.sup.a or Z.sup.a2, and the second hydrocarbon
chain-containing group represented by Z.sup.a2 can be appropriately
selected from the groups described above.
In particular, Z.sup.a2 is preferably a second hydrocarbon
chain-containing group or --O-- group, and especially preferably
--O-- group.
Preferable examples of the structure (a) may include structures
represented by the following formulae (1-1) to (1-32) for
example.
##STR00004## ##STR00005## ##STR00006## ##STR00007## ##STR00008##
##STR00009##
In a coating film obtained using the water/oil-repellent coating
composition of the present invention, the second hydrocarbon
chain-containing group, a hydroxy group, an alkoxy group, or a
group formed via condensation of hydroxy group may be bonded to a
silicon atom (second silicon atom) that originates from the metal
compound (B) and is different from the silicon atom to which the
first hydrocarbon chain-containing group is bonded. The second
silicon atom may be replaced by other metal atom (e.g., Al, Fe, In,
Ge, Hf, Si, Ti, Sn, Zr or Ta). The second silicon atoms or other
metal atoms also behave as a spacer to enhance the water/oil
repellency characteristics of the first hydrocarbon
chain-containing group since the second hydrocarbon
chain-containing group with a carbon number smaller than that of
the first hydrocarbon chain-containing group, a hydroxy group, an
alkoxy group or a hydroxy group is bonded to the second silicon
atoms or other metal atoms.
The carbon number of the alkoxy group is preferably 1 to 4, more
preferably 1 to 3. Examples of the alkoxy group include butoxy
group, propoxy group, ethoxy group and methoxy group.
The hydroxy group may be condensed with other hydroxy group, an
alkoxy group or the like to form --O-- group, and such a group
formed by condensation of a hydroxy group may be bonded to the
metal atoms.
The structure in which the second hydrocarbon chain-containing
group or a hydroxy group is bonded to the second silicon atom or
other metal atom is preferably a structure (B) represented by the
following formula (2).
##STR00010##
wherein R.sup.b2 represents the second hydrocarbon chain-containing
group, hydroxy group or --O-- group,
A.sup.b2 represents hydroxy group or --O-- group,
M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr or Ta, and
n represents an integer of 0 to 3 according to the kind of M.
In the formula (2), the second hydrocarbon chain-containing group
represented by R.sup.b2 can be appropriately selected from the
groups described above.
R.sup.b2 is preferably hydroxy group.
In the formula (2), M is preferably a trivalent metal such as Al, a
tetravalent metal such as Si, Ti, Sn or Zr, more preferably Al, Si,
Ti, Zr, especially preferably Si.
Further, in the formula (2), n represents 1 when M is a trivalent
metal such as Al, Fe or In, n represents 2 when M is a tetravalent
metal such as Ge, Hf, Si, Ti, Sn or Zr, and n represents 3 when M
is a pentavalent metal such as Ta.
Preferable examples of the structure (b) include structures
represented by the following formulae (2-1) to (2-11) when M is
Si.
##STR00011## ##STR00012##
In the resulting coating film, the abundance ratio of the structure
(a) to the structure (b) as structure (a)/structure (b) is
preferably not less than 0.01, more preferably not less than 0.02,
further preferably not less than 0.03, and is preferably not more
than 0.3, more preferably not more than 0.2, further preferably not
more than 0.1, still more preferably not more than 0.09 in terms of
moles.
The thickness of a coating film obtained using the
water/oil-repellent coating composition of the present invention is
preferably not more than 50 nm, more preferably not more than 40
nm. When the thickness of the coating film is not more than 50 nm,
pencil hardness can be increased while abrasion resistance is
maintained. The thickness of the resulting coating film is
preferably not less than 6 nm. When the thickness of the coating
film is not less than 6 nm, the water/oil repellency is effectively
exhibited.
The coating film obtained from the water/oil-repellent coating
composition of the present invention exhibits excellent hardness.
The hardness of the coating film can be evaluated on the basis of,
for example, pencil hardness, and is preferably greater than or
equal to 2H, more preferably greater than or equal to 4H, further
preferably greater than or equal to 7H, and is normally preferably
not greater than or equal to 9H.
Further, a coating film obtained using the water/oil-repellent
coating composition of the present invention comprises a
network-like backbone in which silicon atoms and the metal atoms
(preferably only silicon atoms) are bonded via oxygen atoms. The
coating film comprises a structure in which the first hydrocarbon
chain-containing group is bonded to a part of silicon atoms forming
the backbone. Therefore, the coating film exhibits excellent liquid
droplet slide behavior and water/oil repellency. The liquid droplet
slide behavior can be evaluated using as an index the movement
speed of a liquid droplet sliding down over a coating film formed
on a smooth substrate that is placed so as to be inclined at a
certain angle. In a coating film obtained using the
water/oil-repellent coating composition of the present invention,
the movement speed of a liquid droplet when a substrate provided
with the coating film is inclined at 32.degree. is preferably not
less than 5 cm/sec, more preferably not less than 10 cm/sec,
further preferably not less than 15 cm/sec. The movement speed of a
liquid droplet is described in the following. First, a substrate
provided with a coating film is inclined at 32.degree., and 20
.mu.L of a water droplet is dropped onto the coating film
(hereinafter, sometimes referred to as a position (1)). A location
(hereinafter, sometimes referred to as a position (2)) to which the
liquid droplet slides down by 0.9 cm from the position (1) is
defined as a starting point, and the time required for movement to
a location (hereinafter, sometimes referred to as a position (3))
to which the liquid droplet slides down by 3 cm from the starting
point is measured. The movement distance as 3 cm between the
position (2) and the position (3) is divided by the time required
for sliding-down from the position (2) to the position (3), thereby
determining the movement speed of the liquid droplet.
The coating film of the present invention is formed by coating the
water/oil-repellent coating composition on the substrate. The
substrate may be in the form of a flat surface or a curved surface,
or may have a three-dimensional structure in which a large number
of surfaces are combined. The substrate may be formed of an organic
material or an inorganic material. Examples of the organic material
include thermoplastic resins such as acrylic resin, polycarbonate
resin, polyester resin, styrene resin, acryl-styrene copolymer
resin, cellulose resin, polyolefin resin and polyvinyl alcohol
resin; and thermosetting resins such as phenol resin, urea resin,
melamine resin, epoxy resin, unsaturated polyester, silicone resin
and urethane resin. Examples of the inorganic material include
ceramics; glass; metals such as iron, silicon, copper, zinc and
aluminum; and alloys including the above metals.
The substrate may be subjected to an easy adhesion treatment
beforehand. Examples of the adhesion treatments include
hydrophilization treatments such as a corona treatment, a plasma
treatment and an ultraviolet-ray treatment. A primer treatment with
a resin, a silane coupling agent, a tetraalkoxysilane or the like
may also be employed. By providing a primer layer between a
water-repellent film and a substrate by the primer treatment,
durability such as moisture resistance and alkali resistance can be
further improved.
The primer layer is preferably a layer formed using an under-layer
forming composition containing a component (P) capable of forming a
siloxane backbone.
The primer layer is preferably a layer formed using an under-layer
forming composition containing a component (P1) composed of a
compound represented by the following formula (III), and/or a
partial hydrolysis condensation product thereof. Si(XP.sup.2).sub.4
(III)
wherein each of X.sup.P2 represents a halogen atom, an alkoxy group
or isocyanate group.
In the formula (III), X.sup.P2 is preferably a chlorine atom, an
alkoxy group with a carbon atom number of 1 to 4, or isocyanate
group, and four X.sup.P2s are preferably the same.
Specifically, Si(NCO).sub.4, Si(OCH.sub.3).sub.4,
Si(OC.sub.2H.sub.5).sub.4 or the like is preferably used as the
compound represented by the general formula (III) (hereinafter,
sometimes referred to as a compound (III)). In the present
invention, the compounds (III) may be used singly, or used in
combination of two or more thereof.
The component (P1) contained in the primer layer forming
composition may be a partial hydrolysis condensation product of the
compound (III). The partial hydrolysis condensation product of the
compound (III) can be obtained by applying a general hydrolysis
condensation method using an acid or base catalyst. The degree of
condensation (degree of polymerization) of the partial hydrolysis
condensation product is required to be a degree which allows a
product to be dissolved in a solvent. The component (P1) may be the
compound (III), or a partial hydrolysis condensation product of the
compound (III), or may be a mixture of the compound (III) and a
partial hydrolysis condensation thereof, for example, a partial
hydrolysis condensation product of the compound (III) containing an
unreacted part of the compound (III). As the compound represented
by the general formula (III) or the partial hydrolysis condensation
product, a commercial product is available, and such a commercial
product can be used in the present invention.
The under-layer forming composition may be a composition containing
the component (P1), and a component (P2) composed of a compound
represented by the following formula (IV) (hereinafter, referred to
as a compound (IV)) and/or a partial hydrolysis condensation
product thereof, or a composition containing a partial hydrolysis
co-condensation product of the component (P1) and component (P2)
(which may contain the component (P1) and/or the compound (IV)).
X.sup.P3.sub.3Si--(CH.sub.2).sub.p--SiX.sup.P3.sub.3 (IV)
wherein each of X.sup.P3 represents a hydrolyzable group or hydroxy
group, and p is an integer of 1 to 8.
The compound (IV) is a compound having a hydrolyzable silyl group
or silanol group at both ends of a divalent organic group.
Examples of the hydrolyzable group represented by X.sup.P3 in the
formula (IV) include the same group or atom as X.sup.P2. X.sup.P3
is preferably an alkoxy group or isocyanate group, especially
preferably an alkoxy group from the viewpoint of stability of the
compound (IV) and ease of hydrolysis. The alkoxy group is
preferably an alkoxy group with a carbon atom number of 1 to 4,
more preferably methoxy group or ethoxy group. These groups are
appropriately selected according to the purpose, use and the like
in production. A plurality of X.sup.P3 existing in the compound
(IV) may be the same or different, and is preferably the same from
the viewpoint of easy availability.
Specific examples of the compound (IV) include
(CH.sub.3O).sub.3SiCH.sub.2CH.sub.2Si(OCH.sub.3).sub.3,
(OCN).sub.3SiCH.sub.2CH.sub.2Si(NCO).sub.3,
Cl.sub.3SiCH.sub.2CH.sub.2SiCl.sub.3,
(C.sub.2H.sub.5O).sub.3SiCH.sub.2CH.sub.2Si(OC.sub.2H.sub.5).sub.3,
(CH.sub.3O).sub.3SiCH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2Si(OCH-
.sub.3).sub.3, or the like. In the present invention, the compounds
(IV) may be used singly, or used in combination of two or more
thereof.
The component contained in the primer layer forming composition may
be a partial hydrolysis condensation product of the compound (IV).
The partial hydrolysis condensation product of the compound (IV)
can be obtained by the same method as described in the production
of the partial hydrolysis condensation product of the compound
(III). The degree of condensation (degree of polymerization) of the
partial hydrolysis condensation product is required to be a degree
which allows a product to be dissolved in a solvent. The component
(P) may be the compound (IV), or the partial hydrolysis
condensation product of the compound (III), or may be a mixture of
the compound (IV) and a partial hydrolysis condensation thereof,
for example a partial hydrolysis condensation product of the
compound (IV) containing an unreacted part of the compound
(IV).
As the compound represented by the general formula (IV) or the
partial hydrolysis condensation product, a commercial product is
available, and such a commercial product can be used in the present
invention.
For the under-layer, various kinds of polysilazanes capable of
forming an oxide film mainly composed of silicon, which is similar
to the compound (III), may be used.
The primer layer forming composition normally contains an organic
solvent in addition to a solid as a layer forming component in
consideration of economic efficiency, workability and ease of
controlling the thickness of the obtained primer layer. The organic
solvent is not particularly limited as long as it is capable of
dissolving a solid contained in the primer layer forming
composition. Examples of the organic solvent include the same
compounds as in the water-repellent film forming composition. The
organic solvent is not limited to one kind of solvent, and two or
more solvents different in polarity, vaporization rate and so on
may be mixed and used.
When the primer layer forming composition contains a partial
hydrolysis condensation product and a partial hydrolysis
co-condensation product, the primer layer forming composition may
contain a solvent used for producing these condensation
products.
Further, it is preferable that for accelerating a hydrolysis
co-condensation reaction, a catalyst such as an acid catalyst which
is similar to one that is generally used in a partial hydrolysis
condensation reaction is blended even in a primer layer forming
composition which does not contain a partial hydrolysis
condensation product and a partial hydrolysis co-condensation
product. In the case where the primer layer forming composition
contains a partial hydrolysis condensation product and a partial
hydrolysis co-condensation product, a catalyst is preferably
blended when a catalyst used in these condensation products does
not remain in the composition.
The under-layer forming composition may contain water for carrying
out a hydrolysis condensation reaction and hydrolysis
co-condensation reaction of the contained component.
As a method for forming an under-layer using the primer layer
forming composition, a known method with an organosilane
compound-based surface treatment agent can be used. For example,
the under-layer forming composition can be applied to a surface of
a base by a method such as brush coating, flow coating, rotation
coating, immersion coating, squeeze coating, spray coating or hand
coating, dried as necessary in the air or a nitrogen atmosphere,
and then cured to form the under-layer. Conditions for curing are
appropriately controlled according to the kind, concentration and
the like of a composition to be used.
Curing of the primer layer forming composition may be performed
concurrently with curing of a water-repellent film forming
composition.
The thickness of the primer layer is not particularly limited as
long as it ensures that moisture resistance, adhesion and barrier
property to an alkali etc. from the substrate can be imparted to a
water-repellent film formed on the primer layer.
Using the water/oil-repellent coating composition of the present
invention, the coating film is obtained that attains both water/oil
repellency and hardness, and the coating film is useful for a
substrate in display devices such as touch panel displays, optical
elements, semiconductor elements, building materials, automobile
components, nanoimprint techniques, solar cell members and so on.
The water/oil-repellent coating composition of the present
invention is suitably used for articles such as bodies, window
glass (windshield, side glass and rear glass), mirrors and bumpers
in transportation equipment such as trains, automobiles,
watercrafts and aircrafts. The water/oil-repellent coating
composition can also be used in outdoor applications such as
building outer walls, tents, solar cell power generation modules,
sound insulating boards and concrete. The water/oil-repellent
coating composition can also be used in fishing nets, bug catching
nets and water tanks. Further, the water/oil-repellent coating
composition can also be used in various kinds of indoor equipment
such as articles of members around kitchens, bathrooms, washbasins,
mirrors and toilets, chandeliers, potteries such as tiles,
artificial marbles, and air conditioners. Further, the
water/oil-repellent coating composition can also be used for
antifouling treatment of tools, inner walls, pipes and so on in
factories. The water/oil-repellent coating composition is also
suitable for goggles, glasses, helmets, pinball games, fibers,
umbrellas, play equipment, soccer balls and so on. Further, the
water/oil-repellent coating composition can also be used as a
deposition preventing agent for various kinds of packaging
materials such as food packaging materials, cosmetic packaging
materials and interiors of pots.
The present application claims the benefit of priority to Japanese
patent application No. 2014-223649 filed on Oct. 31, 2014. The
entire contents of the specification of Japanese patent application
No. 2014-223649 filed on Oct. 31, 2014 are incorporated herein by
reference.
EXAMPLES
The present invention is hereinafter described in more detail in
the following by way of Examples, however, the present invention is
not limited to the following Examples, and modifications which do
not depart from the spirit and scope of the present invention are
allowed and embraced within the technical scope of the present
invention. Hereinafter, "part" and "%" mean "part by mass" and "%
by mass", respectively, unless otherwise noted.
Measurement methods used in examples of the present invention are
as follows.
Measurement of Liquid Droplet Slide Behavior
A substrate provided with a coating film by coating the substrate
with a water/oil-repellent coating composition was inclined at
32.degree., 20 .mu.L of water was dropped onto the substrate, and
the movement speed of the liquid droplet was measured.
Specifically, a liquid droplet was dropped onto the coating film
(position (1)). A location (position (2)) to which the liquid
droplet slid down by 0.9 cm from the position (1) was defined as a
starting point, and the time required for movement to a location
(position (3)) to which the liquid droplet slid down by further 3
cm from the starting point was measured. The movement distance (3
cm) between the position (2) and the position (3) was divided by
the time (seconds) required for sliding-down from the position (2)
to the position (3), thereby determining the movement speed of the
liquid droplet.
Measurement of Abrasion Resistance
A steel wool tester (manufactured by Daiei Seiki Co., Ltd.) was
used. An eraser (MONO ONE DUST CATCH manufactured by Tombow Pencil
Co., Ltd.) was brought into contact with the coating film under a
load of 500 g, an abrasion test was conducted at a rate of 40 r/m
in, and the number of abrasion times until the contact angle was
-15.degree. or less with respect to the initial contact angle was
counted. The maximum number of abrasion times is set to 1500, and a
sample with a contact angle of -15.degree. or less even after 1500
times is evaluated as having abrasion resistance (O).
Measurement of Thickness
The thickness of the coating film was measured using a
non-contact-type surface shape measuring instrument (VertScan
manufactured by Ryoka Systems Inc.).
Measurement of Contact Angle
The contact angle of a coating film surface to water was measured
by a liquid droplet method (liquid amount: 3.0 .mu.L) using a
contact angle meter (DM 700 manufactured by Kyowa Interface Science
Co., LTD.).
Example 1
Eighty-four parts of ethanol as a solvent (C) and 60 parts of
hydrochloric acid (0.01 mol/L aqueous solution) as a catalyst were
mixed with 2.8 parts (0.01 parts by mol) of octyltriethoxysilane as
an organosilicon compound (A) and 41.7 parts (0.20 parts by mol) of
tetraethyl orthosilicate (tetraethoxysilane) as a metal compound
(B), and the mixture was stirred at room temperature for 24 hours
to obtain a water/oil-repellent coating composition. The obtained
water/oil-repellent coating composition was applied onto a glass
substrate ("EAGLE XG" manufactured by Corning Incorporated) by spin
coating under the condition of a rotation number of 3000 rpm and 20
sec using a spin coater manufactured by MIKASA Corporation, and
then dried to obtain a coating film.
Examples 2 to 4 and Comparative Examples 1 to 3
A coating film was obtained in the same procedure as in Example 1
except that the kinds and use amounts of the organosilicon compound
(A), the metal compound (B) and the solvent (C) were as shown in
Table 1.
The contact angle to water, and the thickness, the abrasion
resistance and the liquid droplet slide behavior for each of the
obtained coating films are shown in Table 1.
TABLE-US-00001 Comparative Examples Examples 1 2 3 4 1 2 3 Film
Component Organosilicon Octyltriethoxysilane Parts by mol 0.01 0.01
0.01 0.01 production compound (A) (276.49 g/mol) Parts 2.8 2.8 2.8
2.8 Decyltriethoxysilane Parts by mol 0.01 0.01 0.01 (304.54 g/mol)
Parts 3.0 3.0 3.0 Metal Tetraethoxysilane Parts by mol 0.20 0.48
0.187 0.354 0.04 0.08 0.04 compound (B) (208.33 g/mol) Parts 41.7
100.0 39.0 73.7 8.3 16.7 9.2 Solvent (C) Ethanol Parts 84 193.6
81.4 146.2 22.0 37.9 25 Catalyst 0.01 mol/L Parts 60.0 137.0 55.0
102.0 13.5 24.0 15 Hydrochloric acid Physical Contact angle (water)
.degree. 106.2 107.0 109.1 108.8 105.2 106.8 108.2 property
Thickness nm 16.5 200 280 205.0 316 225 327 Abrasion resistance
Times .smallcircle. .smallcircle. .smallcircle. .smal- lcircle.
<100 300 <100 Slide behavior (movement speed of the liquid
droplet. cm/sec 23.1 21.2 23.4 22.2 24.6 23.1 14.17 water 20
.mu.m)
The results described above show that a coating film attaining both
water/oil repellency and abrasion resistance can be obtained using
the water/oil-repellent coating composition of the present
invention.
INDUSTRIAL APPLICABILITY
Using the water/oil-repellent coating composition of the present
invention, the water/oil-repellent coating composition the coating
film attaining both water/oil repellency and abrasion resistance is
obtained, and is useful for fields in display devices such as touch
panel displays, optical elements, semiconductor elements, building
materials, automobile components, nanoimprint techniques, solar
cell members and so on.
* * * * *
References